ES2085268T5 - ENZYMATIC DETERGENT COMPOSITION. - Google Patents

Abstract

A DETERGENT COMPOSITION IS DISCOVERED WHICH UNDERSTANDS (A) AT LEAST AN ACTIVE SURFACE AGENT AND (B) AT LEAST ONE SELECTED ALMIDON ENVELOPE FROM THE GROUP COMPOSED BY PULULANASE, ISOPULULANASE AND ISOAMYLASE. THE DETERGENT COMPOSITION OF THE INVENTION MAY ALSO CONTAIN (ALPHA) -AMILASE, AS A COMPONENT (C). THE DETERGENT COMPOSITION OF THE INVENTION SHOWS SIGNIFICANTLY IMPROVED DETERGENT PROPERTIES AGAINST DIRT.

Description

Enzymatic detergent composition.

This invention relates to a composition. detergent containing at least one surfactant, an enzyme and a inorganic alkaline substance.

It is an already conventional practice to incorporate enzymes in detergent compositions. Enzymes in the detergent compositions serve as auxiliary detergents or washing promoters. Thus, for example, the enzymes in laundry detergent compositions break down or they denature various kinds of dirt (or dirt) and stains adhered to clothing, and enzymes in detergent compositions for dishwashing they break down or denature fat and oils, proteins, starch and the like that remain on the surface of the dishes, which facilitates and promotes the removal of different kinds of dirt.

GB-A-1 293 613 describes a liquid detergent composition comprising 0.001% a 5% by weight of a proteolytic enzyme, amylolytic enzyme, enzyme lipolytic, or a mixture thereof, optionally together with one or more enzyme carriers, and at least 88% by weight of a material 100% essentially active stable liquid detergent, and water Representing the balance. There may also be a surfactant in said detergent composition.

Improved detergency can be achieved dipping the items to be washed in a washing solution containing α-amylase for a period prolonged time However, the α-amylase can hardly work in a satisfactory extension within an ordinary wash time of 5 30 minutes

JP-A-63-119 408 describes a cosmetic composition that contains an enzyme starch hydrolyzate in the form of a powder. The enzyme is, by example, α-amylase, β-amylase, glucoamylase, isoamylase or pululanase

To keep up with the recent fast development of automatic dishwashers not only among restaurants and other commercial facilities but also between homes, detergent compositions have been developed for use in automatic dishwashers. Thus, for example, the detergent compositions for automatic dishwashers, which are commercially available in powder form and constitute a class typical among detergent compositions for washing tableware, comprising, as major components, substances or inorganic alkaline boosters, such as pyrophosphates, tripolyphosphates, orthophosphates, carbonates, bicarbonates, sesquicarbonates, silicates and borates, and, as components minority, surfactants or lipases to improve the detergency of oily or oily dirt, α-amylase for improve, detergency to starch dirt, protease for improve detergency to protein dirt, agents bleaches to improve detergency to pigment stains (e.g. tea stains), as necessary or desired. In the detergent compositions for automatic dishwashers liquid, surfactants are the major components, adding enzymes and other ingredients in small quantities.

The incorporation of α-amylase and similar enzymes in automatic dishwashing detergent compositions, however, not yet satisfactory for dirt removal starch firmly adhered to the dishes within a short time frame. Improvements are desired.

Thus, the invention provides a composition. for laundry and automatic dishwashing comprising at least one surfactant, which is characterized in that it contains at least one starch de-branching enzyme selected from the group consisting of pululanase, and isoamylase, and containing at least one substance inorganic alkaline in an amount so that the wash solution, when it contains the detergent composition in a concentration of 0.05 to 1% by weight, have a pH of 9.0 to 11.0.

The detergent compositions of the invention also preferably contain α-amylase as component (c).

The detergent compositions of the invention contain component (a), namely at least one surfactant, preferably in an amount of 0.5% to 60% by weight based on the composition although the content of component (a) is not limited at any particular level or interval.

Surfactants that can be used as component (a) in the detergent composition of the invention include:

Anionic surfactants such as acid salts alkylbenzenesulfonic, alkyl or alkenyl ether sulfate salts, alkyl or alkenyl sulfate salts, olefinsulfonic acid salts, salts of alkanesulfonic acid, salts of saturated fatty acids or unsaturated, alkyl or alkenyl carboxylic acid salts, salts or esters of α-sulfo fatty acids, amino acid type surfactants, type surfactants N-acyl amino acids, acid phosphate esters of alkyl or alkenyl or salts thereof;

Amphoteric surfactants such as surfactants of carboxy- or sulfobetaine type;

Nonionic surfactants such as ethers of polyoxyalkylene alkyl or alkenyl, polyoxyethylene ethers alkylphenyl; higher fatty acid alkanolamides or adducts of alkylene oxide derivatives thereof, fatty acid esters of sucrose, glycerin monoesters of fatty acids and oxides of alkylamine; Y

Cationic surfactants such as salts of quaternary ammonium

When the detergent composition of the invention It is used as a dishwashing detergent composition automatic, such as component (a), namely at least one surfactant, low or low ionic surfactants are preferred no foaming

Examples of such a surfactant include alkoxylated nonionic surfactants (ethoxylated with oxide of ethylene (EO), propoxylated with propylene oxide or ethoxylated and mixed propoxylates). Preferred examples of said Surfactants are PLURAFAC® LF403 (manufactured by BASF Japan), PLURAFAC® LF1300 (manufactured by BASF Japan) and SOFTANOL® EP7045 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd).

To use the detergent composition of the invention as a dishwashing detergent composition automatic, a surfactant is contained in an amount of preferably 0.5 to 30% by weight based on the composition.

Component (b), namely the starch branching enzyme to be used in the composition of the invention, can be obtained from various sources. Generally, however, it comes from microorganisms. The species of the starch de-branching enzyme are pululanase, and isoamylase, which show amylopectin 6-glucanhydrolase activity, from, for example, microbial strains belonging to the genus Klebsiella, Bacillus, Aspergillus or Pseudomonas .

These enzymes are obtained commercially and examples thereof include SPLENTASE® (manufactured by Amano Pharmaceutical Co., Ltd.) and PROMOZYME® 200L (manufactured by Novo Industri A / S), as regards pululanase; and "isoamylase" (reagent, manufactured by Seikagaku Kogyo Co., Ltd.), regarding the isoamylase Such starch branching enzymes are they usually supply in the form of granules and have an activity enzymatic of approximately 10 5 to 10 8 units per liter.

The starch branching enzyme is contained in the detergent composition of the invention in a amount of preferably 0.01 to 10% by weight, more preferably from 0.01 to 5% by weight.

In order to improve the detergency for the starchy dirt, the detergent composition of the invention may preferably contain α-amylase, in addition to the essential components (a) and (b) mentioned previously, as component (c).

The α-amylase, which is added as an optional component (c) to the detergent composition of the invention, is an enzyme used so far in the detergent compositions and any species thereof can be used. Among them, α-amylase from Bacillus licheniformis or Bacillus subtilis is preferred, and enzymes can be obtained as commercial products under the name of, for example, TERMAMYL® (manufactured by Novo Industri A / S) and MAXAMYL® (manufactured by Gist-Brocades).

When the α-amylase is additionally used in the detergent composition of the invention, the starch branching enzyme and the α-amylase are contained in the composition in an amount to satisfy the relationship such that a reason for activity (reason for deramifying enzyme activity of starch / α-amylase activity) is in the range of preferably 1/10 3 to 10 8/1, more preferably 1/10 to 10 2/1, as determined by the method of the DNS (3,5-dinitrosalicylic acid). The content total starch branching enzyme and α-amylase in the detergent composition of the invention generally ranges from 0.1 to 10% by weight, preferably between 0.1 and 5% by weight.

In washing operations using the detergent composition of the invention, it is preferable to use the composition in an amount such that the wash solution contains the starch branching enzyme and α-amylase each in an amount of no less than 4 units per liter as expressed in terms of enzymatic activity. Each unit (U) of enzyme activity is defined as the amount of enzyme sufficient to form 1 micromol  (um) of glucose per minute.

For enzyme activity measurements, it They use the following methods.

1) Starch branching enzyme activity Substrate

0.5% pululane solution (by weight).

Preparation of the substrate solution

Pululane (0.5 g) was dissolved in 90 ml of water deionized, and 5 ml of buffer was added 1M Tris-HCl (pH 5.9), and then the volume was taken to 100 ml with deionized water.

Test samples

The substrate solution (0.5 ml) was placed in a test tube, 0.4 ml of buffer and 0.1 ml of a properly diluted enzyme solution and allowed to proceed reaction in a constant temperature bath maintained at 40 ° C for 30 minutes Then, 1 ml of a solution of DNS test and the contents of the test tube were heated in boiling water for exactly 5 minutes to develop color. Then, the tube was immediately cooled in a water bath frost. After cooling, 4 ml of deionized water was added and, after mixing thoroughly, absorbance was quickly measured at 535 nm.

White test

The substrate was placed in a test tube (0.5 ml) and 0.4 ml of the buffer, followed by the addition of 1.0 ml of DNS test solution. Additionally, 0.1 ml of the properly diluted enzyme solution and the test tube was put in boiling water immediately and it warmed in it exactly for 5 minutes to develop the color. Then the tube is immediately cooled in an ice water bath. After the cooling, 4 ml of deionized water was added and, after Mix thoroughly, absorbance was quickly measured at 535 nm.

Construction of the calibration curve

The substrate solution was distributed in 0.5 ml portions and the buffer in 0.4 ml portions in tubes test. Then, glucose solutions were added to the each calibrated in an amount of 0.1 ml so that it provide glucose concentrations of 250 to 1,500 µmoles / liter. Additionally, 1.0 ml of the solution of DNS test to each tube. The subsequent procedure is the same as in test samples. After representing the data thus obtained (abscissa for glucose concentration and ordered for absorbance), the gradient (pending) was determined of the resulting curve and the conversion factor (F) was calculated as follows:

F = \ frac {1} {Gradient} \ x \ \ frac {1} {30} \ x \ \ frac {1} {0,1}

Activity Calculation

Enzymatic activity was calculated by next equation

Exercise (U / liter) = δ absorbance x F x Factor of dilution

where δ absorbance = (absorbance for the sample) - (absorbance for the sample White).

2) α-amylase activity Substratum

0.5% solution by weight soluble starch (manufactured by Merck Inc.).

Preparation of the substrate solution

Soluble starch (0.5 g) was dissolved in 90 ml of deionized water, 5 ml of buffer was added 1M Tris-HCl (pH 5.9) and the volume was brought to 100 ml With deionized water.

Test samples

The substrate solution (0.9 ml) was placed in a test tube, followed by the addition of 0.1 ml of a solution of properly diluted enzyme. Then the reaction was allowed to proceed. in a constant temperature bath maintained at 50 ° C for 15 minutes Then, 1 ml of test solution solution was added of DNS and the contents of the test tube were heated in water to boil exactly for 5 minutes to develop the color e immediately after they were cooled in an ice water bath. After cooling, 4 ml of deionized water was added and then of mixing thoroughly, absorbance was quickly measured at 535 nm.

White test

The substrate solution (0.9 ml) was placed in a test tube and then 1.0 ml of the test solution was added of DNS. Additionally, 0.1 ml of the enzyme solution was added properly diluted. The test tube was quickly put in boiling water and heated in it exactly for 5 minutes For color development. After cooling immediately in a ice water bath, 4 ml of deionized water was added and, after mixing thoroughly, absorbance was quickly measured at 535 nm.

Construction of the calibration curve

The substrate solution was distributed in 0.9 ml portions in test tubes. Then they were added glucose solutions for calibration each in an amount of 0.1 ml to provide glucose concentrations of 250 to 1,500 um / liter. Additionally, 1.0 ml of the solution of DNS test to each tube. The subsequent procedure is the same as in the test of the samples. The data thus obtained is represented (abscissa for glucose concentration, ordered for absorbance) and the gradient was determined. The conversion curve (F) It was determined as follows:

F = \ frac {1} {Gradient} \ x \ \ frac {1} {15} \ x \ \ frac {1} {0,1}

Activity calculation

The activity was calculated as follows:

Exercise (U / liter) = δ absorbance x F x Factor of dilution

where δ absorbance = (absorbance for sample) - (absorbance for White).

Preparation of the test solution (1 liter) of acid 3,5-dinitrosalicylic (DNS)

Sodium hydroxide (16 g) was dissolved in 200 ml of deionized water. To the solution 5 g of portions were added in portions DNS After the dissolution of the DNS was completed, 300 were added g of potassium and sodium tartrate. After completing the solution of potassium and sodium tartrate, the volume was brought to 1,000 ml with deionized water.

The detergent composition of the invention can contain other ingredients generally incorporated in conventional detergent compositions depending on the intended use of the detergent composition without particular limitations. These ingredients are described below.

(1) Alkaline substances that are present in detergent compositions such as carbonates, bicarbonates, silicates, borates and alkanolamine salts; or electrolytes inorganic such as sulfates, are incorporated in the composition generally in an amount of 0 to 90% by weight.

(2) Metal ion sequestering agents divalents, for example, phosphates such as tripolyphosphates, pyrophosphates and orthophosphates; phosphonates such as ethane-1,1-diphosphonates; phosphonocarboxylates such as 2-phosphonobutane-1,2-dicarboxylates; amino acid salts such as aspartates and glutamates; amino-polyacetates such as nitrilotriacetates and ethylenediaminetetraacetates; high weight chelating agents molecular such as polyacrylic acid and polyaconitic acid; you go out of organic acids such as oxalates and citrates; Y aluminosilicates, are incorporated into the composition generally in an amount of 0 to 50% by weight.

(3) Bleaching agents such as percarbonate sodium, sodium perborate, sodium hypochlorite and acid dichloroisocyanuric and are incorporated into the composition generally in an amount of 0 to 85% by weight.

(4) Other minority components, which may optionally incorporated into the composition when necessary, include anti-redeposition agents such as polyethylene glycol and carboxymethyl cellulose; enzymes, such as protease, lipase and cellulase; enzyme deactivation inhibitors such as sulphites; fluorescent whitening agents (or brighteners optical); blueing agents; dyes; hardness inhibitors; solubilizing agents, activators for enzymes or agents bleaches; corrosion inhibitors and so on.

For use in automatic dishwashers, the detergent composition of the invention, when in powder form, contains at least one inorganic alkaline substance selected from sodium pyrophosphate, sodium orthophosphate, sodium tripolyphosphate, sodium carbonate, sodium bicarbonate, sesquicarbonate of sodium, borax or sodium silicate. It is preferable to use sodium silicate in combination with one or more other alkaline substances since sodium silicate has corrosion inhibitory activity. The combined use of 2 to 15% by weight of sodium silicate (the SiO2 / Na2O ratio being between 1/1 and 4/1, preferably between 2/1 and 2.5 / 1) and 35 to 85% by weight of one or more other alkaline substances is more preferred. The total inorganic alkaline substance content is adjusted so that the washing solution, when it contains the detergent composition in a concentration of 0.05 to 1% by weight, has a pH of 9.0 to 11.0. In the case of the liquid detergent composition, water counts for the
balance.

In view of the current trend towards phosphate-free detergents to avoid or solve environmental or eutrophication problems, can be important formulate phosphate-free compositions for dishwashing by machine with the development of automatic dishwashers, without no significant decrease in detergency versus Various kinds of dirt. In the formulation of said phosphate free detergent compositions, it is preferable incorporate a hydrogen polycarboxylic acid represented by the following formula (I), or water soluble salts thereof, in the detergent composition of the invention as a sequestering agent of divalent metal ions:

one

where X represents H, -CH_ {3}, -CH 2 COOH or -CH (OH) COOH; e Y represents H u -OH.

Among the compounds represented by the above formula (I) citric acid, malic acid and tartaric acid. Examples of water soluble salts of they include sodium salt, potassium salt, salt of monoethanolamine, diethanolamine salt and triethanolamine salt.

The detergent composition of the invention Contains the hydrogen polycarboxylic acid or soluble salts in water thereof in an amount of preferably 0.5 to 30% in weight.

Additionally, it is preferable for the formulation of said phosphate free detergent composition using an agent high molecular weight chelator as an ion sequestering agent of divalent metals in an amount of 1 to 10% by weight. As soon as to the high molecular weight chelating agent, a sequestering polyelectrolyte of divalent metal ions as se describe in JP-A-57-145199 (the term "JP-A" as used here means "a published Japanese Patent Application not examined"), and Examples thereof include acrylic acid or acid polymers. methacrylic, acrylic acid methacrylic acid copolymers, and water soluble salts of these. Your average molecular weights they will preferably range between 1,500 and 100,000, more preferably  between 3,000 and 20,000.

The dishwashing detergent composition automatic invention may additionally contain conventional ingredients, for example proteolytic enzymes, bleaching agents such as dichloroisocyanuric acid e copper corrosion inhibitors, if necessary.

A preferred example of the proteolytic enzyme that can be used in the composition of the invention is subtilisin, and can be obtained from specific microbial strains belonging to the species Bacillus subtilis or Bacillus licheniformis . Subtilisin is available as commercial products under the name of, for example, MAXATASE® (manufactured by Gist-Brocades), ALCALASE® (manufactured by Novo Industri A / S), ESPERASE® (manufactured by Novo Industri A / S) and SAVINASE ® (manufactured by Novo Industri A / S).

It is also effective to add a fatty acid that have a hydrocarbon chain length of approximately 8 to 18 or benzotriazole or the like as a corrosion inhibitor of copper.

The detergent composition of the invention that contains the starch de-branching enzyme specified here shows a detergency to starch dirt significantly improved within an ordinary washing time. The incorporation additional of a hydroxypolycarboxylic acid or a salt thereof not only markedly improves the detergency of starch dirt but also the detergency of oily or oily dirt.

The following examples are also illustrative of the present invention but does not mean that they limit the scope of the same. In the examples, unless otherwise specified, "%" means "% by weight" and the relationships given are relationships by weight.

Example 1 Detergent compositions for automatic dishwashers

Washing conditions and the method of detergency assessment used in this example and the Results obtained are as follows:

1) Washing conditions

Washing machine: Dishwasher fully NP-600 automatic model manufactured by Matsushita Electric Industrial Co., Ltd. In this model, a solution aqueous detergent released by lava rotating nozzle means the plates and the like placed in the orbital plane of the media nozzle

Washing temperature: The temperature rises gradually from 5ºC to 55ºC.

Washing water: Water that has a hardness of 3.5º DH.

Detergent concentration: 0.2% (being the Enzymatic activity in the 440 U / liter wash solution).

Washing time: Application of the solution Wash 20 minutes, rinse 20 minutes.

Amount of circulating wash solution: 2.5 liters

2) Detergency evaluation Dishes carrying starchy dirt

Rice flour pudding and rice were mixed cooked in a 9: 1 ratio. An equal amount of water was added from the tap to the mixture and the whole was mixed in a mixer. Is dirt mixture (4 g) was applied evenly to a plate of ceramic with a diameter of 22 cm and air dried for a day full.

For each wash test, three were used dirty dishes of the previous form.

Determination of starch dirt detergency

Residual starch was determined by reaction of color with iodine followed by determination of the blue colored area  resulting (P_ {1}) by a photograph. The detergency is calculates compared to the area of the dirty surface initial (S_ {0}) using the following equation:

Detergency (%) = ((S_ {0} - P_ {1}) / S_ {0}) \ x \ 100

3) Detergent composition formulation

SOFTANOL EP 7045 two Citrate of sodium twenty Sodium silicate, grade No. one 5 Enzyme See table one Carbonate sodium Balance Note: The numerical values are in% in weigh.

4) Results of the detergency test

The results obtained are shown in the Next Table 1, in which Compositions Nos. 1 to 3 are of the The present invention and Nos. 4 and 5 are for comparison.

TABLE 1

two

Notes: 1) Pululanase, manufactured by Amano Pharmaceutical Co., Ltd .; 6.1x106 U / liter 2) Pululanase, manufactured by Novo Industri A / S; 4.5x105 U / liter 3) Isoamylase, manufactured by Seikagaku Kogyo Co., Ltd .; 5.9x10 7 U / liter 4) α-amylase, manufactured by Novo Industri A / S; 4.4x10 7 U / liter 5) α-amylase, manufactured by Gist-Brocades; 7.2x106 U / liter

Example 2 Laundry detergent compositions

Washing conditions and test method of detergency used in this example and the results obtained They are as follows:

1) Artificially soiled clothes

Rice flour pudding and rice were combined cooked in a 9: 1 ratio. After a double dilution with tap water, the whole was mixed in a mixer. Mix resulting was applied to test pieces of cotton fabric with a size 10 cm x 10 cm at a level of 2.5 to 5% based on the weight of the tissue. The soiled tissues were dried at 20 ° C for 24 hours and then rehearsed.

2) Washing conditions and method

The detergent composition (in powder form) a test was dissolved in hard water (4th DH) to give 1 liter of a 0.665% aqueous detergent solution (enzymatic activity of the wash solution 1.98 x 10 3 U / liter). Five pieces of fabric artificially soiled cotton test were placed in the washing solution and, after 1 hour of permanence at 40 ° C, the wash solution and soiled test pieces artificially transferred to the stainless steel bucket of a "Terg-o-Tometer." It took wash out in the "Terg-o-Tometer" at 20 ° C for 10 minutes with stirring at 100 rpm. After rinsing with water current, the test pieces were dried at 20 ° C for 24 hours and then weighed.

3) Detergency evaluation

The detergency (%) was calculated based on the weight of the five pieces of test tissue before fouling (weight original), its weight after fouling (weight before washing) and its weight after washing, using the following equation:

Detergency (%) = \ frac {(Weight \ before \ to wash) - (Weight \ after \ to \ wash)} {(Weight \ before \ wash) - (Weight \ original)} x 100

Each of the detergency values given in Table 2 is the average for five test pieces.

4) Detergent composition formulation

n-Dodecylbenzenesulfonate of sodium fifteen Alkylethoxylate sulfate sodium 5 (C_ {14} -C_ {15}, EO = 3 moles) Zeolite type 4A fifteen Silicate sodium fifteen Carbonate sodium fifteen Sodium Polyacrylate (PM = 8,000) 1.5 Polyethylene glycol (PM = 6,000) 1.5 Enzyme See table two Rinse aid optical 0.5 Sulfate sodium Balance Water 5 Note: The numerical values are in% in weigh.

5) Results of the detergency test

The test results obtained are shown in Table 2, in which Compositions Nos. 1 to 3 are of the The present invention and Nos. 4 and 5 are for comparison.

TABLE 2

3

Example 3 Automatic dishwashing detergent compositions 1) Washing conditions

The same as in Example 1.

2) Dishes soiled with cooked rice and method of evaluation Dirty dishes

Cooked rice, freshly boiled to a soft consistency at room temperature for 30 minutes, then it was applied, crushing it, to ceramic plates with a diameter of 25 cm (3 g of cooked rice per plate), and dried for a full day at room temperature. For each trial of washed, 6 soiled dishes were used as above.

Determination of starch dirt detergency

As in Example 1.

3) Detergent composition formulation

SOFTANOL EP7045 2.0 Tripolyphosphate sodium 20.0 Sodium silicate, grade No. one 5.0 Enzyme See table 3 Carbonate sodium Balance Note: The numerical values are in% in weigh.

4) Results of detergency tests

The results of the tests obtained are shown in Table 3, in which Compositions Nos. 1 to 4 are of the present invention and Nos. 5 and 6 are for comparison.

4

Example 4 Laundry detergent compositions

Washing conditions and test method of detergency used in this example and the results obtained They are as follows:

1) Artificially soiled fabric

Cooked rice was diluted twice with water from tap and subjected to mixing in a mixer. The resulting mass It was applied to test pieces of cotton fabric with a size of 10 cm x 10 cm with a weight gain of 2.5 to 5% based on the weight of the tissue, then dried at 20 ° C for 24 hours and tested.

2) Washing conditions and method

The same as in Example 2.

3) Detergency evaluation

As in Example 2.

4) Detergent composition formulation

n-Dodecylbenzenesulfonate of sodium fifteen Alkylethoxylate sulfate sodium (C 14 -C 15, EO = 3 moles) 5 Zeolite Type 4A fifteen Silicate sodium fifteen Carbonate sodium fifteen Sodium Polyacrylate (PM = 8,000) 1.5 Polyethylene glycol (PM = 6,000) 1.5 Enzyme See table 4 Rinse aid optical 0.5 Sulfate sodium Balance Water 5 Note: The numerical values are in% in weigh.

5) Results of detergency tests

The results of the tests obtained are shown in Table 4, where Composition 1 is of the present invention and Composition 2 is for comparison.

TABLE 4

5

Example 5 Automatic dishwashing detergent compositions 1) Washing conditions

The same as in Example 1.

2) Detergency evaluation (1) Dishes soiled with grease and method of evaluation Dirty dishes

Cow tallow (5 g) was applied to each of the ceramic plates (25 cm in diameter) and air dried for a full day For each trial, 2 dishes were used.

Determination of grease dirt detergency

After washing, a solution of Red oil on each plate. The area so colored (S_ {1}) on each dish was measured by a photograph and compared to the area initial soiled (S_ {0}). The detergency was calculated by next equation

Detergency (%) = ((S_ {0} - S_ {1}) / S_ {0}) x 100

(2) Dishes soiled with rice and method of evaluation Dirty dishes

As in Example 3.

Determination of starch dirt detergency

As in Example 1.

The compositions specified in Table 5 below and were evaluated for detergency by the evaluation methods mentioned above. The results obtained are also shown in Table 5.

In Table 5, Compositions Nos. 1 and 2 are for comparison, while the other compositions fall within of the scope of the present invention. Of the data shown in the Table 5, it is evident that the combined use of the components (a), (b) and (c) of the present invention can produce an effect significant synergistic

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Although the invention has been described in detail and with reference to specific embodiments thereof, it will be evident to any person skilled in the art that can be done various changes and modifications in it without departing from the scope Of the same.

Claims (17)

1. An automatic dishwashing detergent composition comprising at least one surfactant, which is characterized in that it contains at least one starch branching enzyme selected from the group consisting of pululanase, and isoamylase, and containing at least one alkaline inorganic substance in an amount so that the Washing solution, when it contains the detergent composition in a concentration of 0.05 to 1% by weight, has a pH of 9.0 to 11.0. 2. The dishwashing detergent composition automatic of claim 1, wherein said composition contains additionally α-amylase. 3. The dishwashing detergent composition automatic of claim 2, wherein said de-branching enzyme of starch and said α-amylase are contained in an amount that satisfies the relationship such that a ratio of activity of said starch branching enzyme and said α-amylase is 1/10 3 to 10 8/1, as It is determined by the DNS method. 4. The dishwashing detergent composition automatic of claim 3, wherein said de-branching enzyme of starch and said α-amylase are contained in an amount to satisfy the relationship such that a reason for activity of said starch branching enzyme and said α-amylase is 1/10 to 10 2/1, as determined by the DNS method. 5. The dishwashing detergent composition automatic of claim 1, wherein said surfactant is present in an amount of 0.5 to 60% by weight and said enzyme starch de-branching agent is present in an amount of 0.01 to 10% by weight. 6. The dishwashing detergent composition automatic of claim 2, wherein said surfactant is present in an amount of 0.5 to 60% by weight and said enzyme starch and said α-amylase de-branching agent they are present in a total amount of 0.1 to 10% by weight. 7. The dishwashing detergent composition automatic of claim 2, wherein said composition detergent additionally contains a hydroxypolycarboxylic acid or a salt thereof. 8. The dishwashing detergent composition automatic of claim 7, wherein said surfactant is present in an amount of 0.5 to 30% by weight, said enzyme starch and said α-amylase de-branching agent they are present in a total amount of 0.1 to 5% by weight, and said hydroxypolycarboxylic acid or a salt thereof is present in an amount of 0.5 to 30% by weight. 9. A laundry detergent composition comprising at least one surfactant, which is characterized in that it contains at least one starch branching enzyme selected from the group consisting of pululanase, and isoamylase and because it contains at least one alkaline inorganic substance in an amount so that The washing solution when it contains the detergent composition in a concentration of 0.05 to 1% by weight, has a pH of 9.0 to 11.0. 10. The laundry detergent composition of claim 9, wherein said composition contains additionally α-amylase. 11. The laundry detergent composition of claim 10, wherein said de-branching enzyme of starch and said α-amylase are contained in an amount to satisfy the relationship such that a reason for activity of said starch branching enzyme and said α-amylase is from 1/10 3 to 10 8/1, as determined by the DNS method. 12. The laundry detergent composition of claim 11, wherein said de-branching enzyme of starch and said α-amylase are contained in an amount to satisfy the relationship such that a ratio of activity of said starch branching enzyme and said α-amylase is 1/10 to 10 2/1, as determined by the DNS method. 13. The laundry detergent composition of claim 9, wherein said surfactant is present in a amount of 0.5 to 60% by weight and said de-branching enzyme of Starch is present in an amount of 0.01 to 10% by weight. 14. The laundry detergent composition of claim 10, wherein said surfactant is present in an amount of 0.5 to 60% by weight and said de-branching enzyme of starch and said α-amylase are present in a total amount of 0.1 to 10% by weight. 15. The laundry detergent composition of claim 10, wherein said detergent composition contains additionally a hydroxypolycarboxylic acid or a salt of the same. 16. The laundry detergent composition of claim 15, wherein said surfactant is present in an amount of 0.5 to 30% by weight, said de-branching enzyme of starch and said α-amylase are present in a total amount of 0.1 to 5% by weight, and said acid hydroxypolycarboxylic or a salt thereof is present in a amount of 0.5 to 30% by weight. 17. Use of a composition comprising at least a surfactant and at least one starch branching enzyme selected from the group consisting of pululanase, and isoamylase as automatic dishwashing detergent or washing detergent of clothing, where the composition contains at least one substance inorganic alkaline in an amount so that the wash solution, when it contains the detergent composition in a concentration of 0.05 to 1% by weight, has a pH of 9.0 to 11.0.